US3478154A - Fungicidal (n-substituted carbamoylmethyl) sulfonium chlorides - Google Patents
Fungicidal (n-substituted carbamoylmethyl) sulfonium chlorides Download PDFInfo
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- This invention relates to new and useful sulfonium halides and to new and useful fi-arylamino cinnamoyl derivatives thereof.
- the sulfonium halides of this invention can be represented by the general formula wherein X is halogen of atomic weight in the range of 35 to 127 (i.e. chlorine, bromine or iodine), wherein R" and R' are like or unlike lower alkyl (i.e. methyl, ethyl, propyl, butyl, and the various isomeric forms thereof containing up to and including four carbon atoms), and wherein A is either lower alkoxy (e.g. methoxy, ethoxy, propoxy, butoxy, and the various isomeric forms thereof containing up to and including four carbon atoms) or, and preferably,
- R-If-R' wherein R is lower alkyl or lower alkenyl or lower alkoxyalkyl (e.g. methyl, ethyl, propyl, butyl, allyl, butenyl, methoxyethyl, ethoxyethyl, methoxypropyl, and the various isomeric forms thereof containing up to and including four carbon atoms) and wherein R is hydrogen or lower alkyl or lower alkenyl or lower alkoxyalkyl (e.g.
- X be chlorine
- R" and R' be C alkyl (i.e. methyl or ethyl) and that both R and R be either like lower n-alkyl or like lower n-alkenyl.
- This preferred group is particularly useful as foliage fungicides, as for example controlling Venturia inaequalis (apple scab).
- the sulfonium chlorides and bromides of this invention are prepared by reacting a sulfide of the formula R"S wherein R" and R' have the aforedescribed significance, with a substantially equimolecular proportion of an a-haloaceto compound of the formula 0 ZCHz-pJ-A wherein Z is chlorine or bromine and wherein A has the aforedescribed significance, in a fluid system (i.e. a reaction temperature above the freezing point of the system up to and including the reflux temperature of the system or the decomposition temperature of the sulfonium halide).
- a fluid system i.e. a reaction temperature above the freezing point of the system up to and including the reflux temperature of the system or the decomposition temperature of the sulfonium halide.
- an inert organic Patented Nov. 11, 1969 solvent can 'be used, e.g.
- the sulfonium iodides are prepared by mixing potassium iodide with a concentrated aqueous solution of the appropriate sulfonium chloride in substantially equimolecular proportions at room temperature, the sulfonium iodide product being less water-soluble than the sulfonium chloride reactant precipitates out and is recovered by simple filtration.
- Exemplary of the sulfide reactants are dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, diisopropyl sulfide, din-butyl sulfide, methylethyl sulfide, ethylisopropyl sulfide, butylmethyl sulfide, and the like.
- a-haloaceto compound reactants are N,N-dimethyl-a-chloroacetamide, N,N-diethyl-a-chloroacetamide, N,N-diisopropyl-a-chloroacetamide, N-methyl-a-chloroacetamide, N-ethyl-a-chloroacetamide, N-allyl-a-chloroacetamide, N,N-diallyl-u-chloroacetarnide, N-allyl-N-methyl-a-chloroacetamide, N-methyl-N-isopropyl-a-chloroacetamide, N,N-di(2-methoxyethyl) -a-chloroacetamide, N,N-di(2-ethoxyethyl)-a-chloroacetamide, N-(2-ethoxyethyl)-a-chloroacetamide, N-n-butyl-a
- fi-arylamino cinnamides are fungicides while the fi-arylamino cinnamoyl compounds are insecticidally active against mosquito larvae.
- the reaction between the sulfonium halide and sodium hydride temperatures in the range of from about 10 C. to about 30 C. will be employed.
- any temperature can be employed which provides a fluid system (i.e. a reaction temperature above the freezing point of the system up to and including the reflux temperature of the system).
- a fluid system i.e. a reaction temperature above the freezing point of the system up to and including the reflux temperature of the system.
- the Schiifs base reactants are benzalaniline, N- (p-methoxybenzylidene) aniline, N- (m-methoxybenzylidene) aniline,
- N- m,p-dimethoxybenzylidene) -o-toluidine N- -p-methoxybenzylidene -p-phenetidine
- N-m-methylb enzylidene N-m-methylb enzylidene
- sulfonium halides and B-arylamino cinnamoyl compounds which can be prepared in accordance with the procedures of this invention include methylethyl (N,N-diallylcarbamoylmethyl sulfonium chloride,
- Slide germination test the concentration of the compound to be evaluated required to inhibit complete germination of spores from 7- to 10-day old cultures of Venturia inaequalis is determined. 1.0 gram of the compound (below itemized) is dissolved in acetone to make a concentrated solution thereof and thereto is added and intimately mixed 0.] gram of sorbitan monolaurate polyoxyethylene derivative (a commercial water-soluble non-ionic emulsifying agent). Thereto is added and intimately mixed sufficient water to provide an aqueous emulsion containing 10 p.p.m. of the compound.
- sorbitan monolaurate polyoxyethylene derivative a commercial water-soluble non-ionic emulsifying agent
- a test tube To a test tube is then added four volumes of the aqueous emulsion and one volume of spore stimulant and one volume of spore suspension, the spore stimulant being added to insure a high and relatively stable percentage of germination in the control.
- Drops of the test specimen mixture and an untreated control are pipetted onto glass slides. The glass slides are then placed in moist chambers for hours incubation at 22 C. Germination counts are made by counting 100 potentially viable spores, i.e. those spores which would germinate under the normal conditions of the control. The results were as follows:
- alkyl ,B-arylamino cinna'mates of this invention effectively control mosquito larvae.
- ethyl 8-anilinocinnamate exhibited a kill of yellow fever mosquito larvae, Aedes aegypti.
- concentration of the fungicidal or insecticidal agents of this invention employed in combatting or controlling fungi o'r insects can vary considerably provided the required dosage (i.e., a toxic amount) thereof is supplied to the respective organisms or to the environment of the organisms.
- the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the fungicidal or insecticidal agent employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight.
- concentration of the fungicidal or insecticidal agent employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight.
- the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared fungicidal or insecticidal spray or particulate solid.
- a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared fungicidal or insecticidal spray or particulate solid.
- the fungicidal or insecticidal agent generally Will be present in a concentration of 5 to percent by weight, the residue being any one or more of the well-known fungicidal or insecticidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent, surface-active clays), solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.
- the various surface active agents e.g., detergents, a soap or other emulsifying or wetting agent, surface-active clays
- solvents e.g., diluents, carrier media, adhesives, spreading agents, humectants, and the like.
- the fungicidal or insecticidal agents of this invention either per se or compositions comprising same are supplied to the fungi or insects or to their environment in a toxic amount. This can be done by dispersing the new fungicidal or insecticidal agent or fungicidal or insecticidal composition comprising same in, on or over an infested environment or in, on or over an environment the fungi or insects frequent, e.g.
- Such dispersing can be brought about by applying the fungicidal agent per se or sprays or particulate solid compositions containing same to a surface infested with the fungi or insects or attractable to same, as for example, the surface of agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g. power dusters, boom and hand sprayers, and spray dusters.
- such dispersing can be carried out by simply mixing the new fungicidal or insecticidal agent per se or fungicidal or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the fungi or insects frequent, or by employing a liquid carrier for the new fungicidal 0r insecticidal agent to accomplish sub-surface penetration and impregnation therein.
- the method of controlling Ven turia inaequalis which comprises contacting same with a fungicidally toxic amount of a sulfonium chloride of the formula RQ R e s-cm-c-a/ 01 wherein R" and R'" are C alkyl and wherein R and R are like lower n-alkyl.
- the method of controlling Venturia inaequalis which comprises contacting same with a fungicidally toxic amount of a sulfonium chloride of the formula wherein R" and R' are C alkyl and wherein R and R are like lower n-alkenyl.
- the method of controlling Venturiw inaequalis which comprises contacting same with a fungicidally toxic amount of dimethyl(N,N diallylcarbamoylmethyl)sulfonium chloride.
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Description
United States Patent 3,478,154 FUNGICIDAL (N -SUBSTITUTED CARBAMOYL- METHYL) SULFONIUM CHLORIDES Kenneth Wayne Ratts, Creve Coeur, Mo., assignor to Monsanto Company, St. Louis, Mo., a corporation of Delaware No Drawing. Filed June 28, 1965, Ser. No. 467,750 Int. Cl. A01n 9/12; C07c 103/10 US. Cl. 424-320 3 Claims ABSTRACT OF THE DISCLOSURE Fungicidal sulfonium chlorides of the formula wherein R" and R are methyl or ethyl and wherein R and R are like lower n-alkyl or like lower n-alkenyl.
This invention relates to new and useful sulfonium halides and to new and useful fi-arylamino cinnamoyl derivatives thereof.
The sulfonium halides of this invention can be represented by the general formula wherein X is halogen of atomic weight in the range of 35 to 127 (i.e. chlorine, bromine or iodine), wherein R" and R' are like or unlike lower alkyl (i.e. methyl, ethyl, propyl, butyl, and the various isomeric forms thereof containing up to and including four carbon atoms), and wherein A is either lower alkoxy (e.g. methoxy, ethoxy, propoxy, butoxy, and the various isomeric forms thereof containing up to and including four carbon atoms) or, and preferably,
R-If-R' wherein R is lower alkyl or lower alkenyl or lower alkoxyalkyl (e.g. methyl, ethyl, propyl, butyl, allyl, butenyl, methoxyethyl, ethoxyethyl, methoxypropyl, and the various isomeric forms thereof containing up to and including four carbon atoms) and wherein R is hydrogen or lower alkyl or lower alkenyl or lower alkoxyalkyl (e.g. methyl, ethyl, propyl, butyl, allyl, butenyl, methoxyethyl, ethoxyethyl, methoxypropyl, and the various isomeric forms thereof containing up to and including four carbon atoms). It is preferred that X be chlorine, that R" and R' be C alkyl (i.e. methyl or ethyl) and that both R and R be either like lower n-alkyl or like lower n-alkenyl. This preferred group is particularly useful as foliage fungicides, as for example controlling Venturia inaequalis (apple scab).
The sulfonium chlorides and bromides of this invention are prepared by reacting a sulfide of the formula R"S wherein R" and R' have the aforedescribed significance, with a substantially equimolecular proportion of an a-haloaceto compound of the formula 0 ZCHz-pJ-A wherein Z is chlorine or bromine and wherein A has the aforedescribed significance, in a fluid system (i.e. a reaction temperature above the freezing point of the system up to and including the reflux temperature of the system or the decomposition temperature of the sulfonium halide). Where and when desired an inert organic Patented Nov. 11, 1969 solvent can 'be used, e.g. benzene, toluene, xylene, hexane, heptane, octane, and the like. The sulfonium iodides are prepared by mixing potassium iodide with a concentrated aqueous solution of the appropriate sulfonium chloride in substantially equimolecular proportions at room temperature, the sulfonium iodide product being less water-soluble than the sulfonium chloride reactant precipitates out and is recovered by simple filtration. Exemplary of the sulfide reactants are dimethyl sulfide, diethyl sulfide, di-n-propyl sulfide, diisopropyl sulfide, din-butyl sulfide, methylethyl sulfide, ethylisopropyl sulfide, butylmethyl sulfide, and the like. Exemplary of the a-haloaceto compound reactants are N,N-dimethyl-a-chloroacetamide, N,N-diethyl-a-chloroacetamide, N,N-diisopropyl-a-chloroacetamide, N-methyl-a-chloroacetamide, N-ethyl-a-chloroacetamide, N-allyl-a-chloroacetamide, N,N-diallyl-u-chloroacetarnide, N-allyl-N-methyl-a-chloroacetamide, N-methyl-N-isopropyl-a-chloroacetamide, N,N-di(2-methoxyethyl) -a-chloroacetamide, N,N-di(2-ethoxyethyl)-a-chloroacetamide, N-(2-ethoxyethyl)-a-chloroacetamide, N-n-butyl-a-chloroacetamide, N,N-di-n-butyl-a-chloroacetamide, and the like,
and the corresponding a-bromoacetamides, and methyl a-chloroacetate, ethyl a-chloroacetate, isopropyl a-chloroacetate, n-butyl a-chloroacetate, isobutyl a-chloroacetate, and the like, and the corresponding a-bromoacetates.
The sulfonium halides of this invention are useful in preparing ,B-arylamino cinnamoyl compounds of the general formula Ar-C=CH A wherein A has the aforedescribed significance and preference, and wherein Ar and Ar are like or unlike aryl having from 6 to 10 carbon atoms such as phenyl, alkylphenyl (e.g. tolyl, xylyl, ethylphenyl, cumyl, cymenyl, *butylphenyl, and the various isomeric forms thereof), and alkoxyphenyl (e.g. anisyl, dimethoxyphenyl, phenetyl, diethoxyphenyl, propoxyphenyl, butoxyphenyl, and the various isomeric forms thereof). The fi-arylamino cinnamides are fungicides while the fi-arylamino cinnamoyl compounds are insecticidally active against mosquito larvae.
The [St-arylamino cinnamoyl compounds of this invention are prepared by initially reacting substantially equimolecular proportions of sodium hydride and a sulfonium halide of the aforedescribed formula under anhydrous conditions in the presence of tetrahydrofuran under a nitrogen atmosphere until an approximately equimolecular amount of hydrogen evolves, and thereafter adding to the reaction mass so obtained under a nitrogen atmosphere a substantially equimolecular amount of a Schifls base of the formula ArCH=NAr' wherein Ar and Ar have the aforedescribed significance. In the reaction between the sulfonium halide and sodium hydride temperatures in the range of from about 10 C. to about 30 C. will be employed. In the reaction involving the Schiffs base any temperature can be employed which provides a fluid system (i.e. a reaction temperature above the freezing point of the system up to and including the reflux temperature of the system). Exemplary of the Schiifs base reactants are benzalaniline, N- (p-methoxybenzylidene) aniline, N- (m-methoxybenzylidene) aniline,
N- (m,p-dimethoxybenzylidene) aniline,
N- (p-ethoxybenzylidene) aniline,
N- (m,p-diethoxybenzylidene) aniline,
N- (p-methylbenzylidene) aniline,
N- (m,m'-dimethylb enzylidene aniline,
N- (p-tert.butylbenzylidene) aniline, benzal-o-toluidine,
benzal-p-anisidine,
benzal-p-phenetidine, benzal-m,p-dimethoxyaniline, benzal-p-methoxy-o-toluidine,
N- m,p-dimethoxybenzylidene) -o-toluidine, N- -p-methoxybenzylidene -p-phenetidine, (N-m-methylb enzylidene) -m,m'-xylidine, and the like.
As illustrative of this invention but not limitative thereof is the following:
EXAMPLE I To a suitable reaction vessel equipped with a thermometer and agitator 75.1 parts by Weight (substantially 1.2 moles) of dimethyl sulfide and 149.6 parts by weight (substantially 1.0 mole) of N,N-diethyl-a-chloroacetamide. The so charged mass is heated at about 40 C. for fourteen hours, filtered and the filter cake dried under anhydrous nitrogen to give 98.9 parts by weight of dimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride.
EXAMPLE II To a suitable reaction vessel equipped with a vent, thermometer and agitator is charged 12.0 parts by weight (substantially 0.05 mole) of dimethyl(N,N-diethylcarbamoylmethyl)sulfonium chloride and 350 parts by weight of anhydrous tetrahydrofuran. While agitating the so charged mass under a nitrogen atmosphere there is added 2.3 parts by weight (substantially 0.05 mole) of sodium hydride in the form of a 53% by weight dispersion in mineral oil. The system is immediately connected to a gas meter to observe the evolution of hydrogen. After agitating for about two hours at room temperature approximately 0.1 part by weight (substantially 0.05 mole) of hydrogen evolved. To the resulting reaction mass and while agitating under a nitrogen atmosphere is added 10.5 parts by weight (substantially 0.05 mole) of N-(p-methoxybenzylidene)aniline. After agitating for one hour at room temperature the mass is then heated at about 60 C. for one hour, whereupon the mass is cooled to room temperature and filtered. The filtrate is evaporated in vacuo and the yellow oily residue crystallized from petroleum ether to give 10.5 parts by weight of fl-anilino-N,N-diethyl-p-methoxycinnamide.
which melts at 108-110" C.
EXAMPLE III Employing the procedure of Example I but replacing N,N-diethyl-u-chloroacetamide with an equimolecular amount of N,N-diethyl-a-hromoacetamide there is obtained dirnethyl(N,N-diethylcarbamoylmethyl)sulfonium bromide.
EXAMPLE IV Employing the procedure of Example II but replacing N-(p-methoxybenzylidene)aniline with an equimolecular amount of N-(m,m-dimethy1benzylidene)aniline there is obtained p-anilino-N,N-diethyl m,m' dimethylcinnamide.
4 EXAMPLE v Employing the procedure of Example II but replacing N-(p-methoxybenzylidene)aniline with an equimolecular amount of benzalaniline [sometimes termed N-(benzylidene)aniline] there is obtained fi-anilino-N,N-diethylcinnamide which melts at 91-92 C.
EXAMPLE VI Employing the procedure of Example I but replacing N,N-diethyl-a-chloroacetamide with an equimolecular amount of N,N-diallyl-a-chloroacetamide there is obtained dimethyl (N,N-diallylcarbamoylmethyl) sulfonium chloride which melts at 12012l C.
EXAMPLE VII Employing the procedure of Example I but replacing N,N-diethyl-a-chloroacetamide with an equimolecular amount of N-n-propyl-a-chloroacetamide there is obtained dimethyl(N-n-propylcarbamoylmethyl)sulfonium chloride, a solid hygroscopic nature.
EXAMPLE IX Employing the procedure of Example II but replacing dimethyl(N,N-diethylcarbamoylmethyl)sulfonium chloride with an equimolecular amount of dimethyl(N-npropylcarbamoylmethyl)sulfonium chloride there is obtained ,B-anilino-N-n-propyl-p-methoxycinnamide.
EXAMPLE X Employing the procedure of Example II but replacing dimethyl(N,N-diethylcarbamoylmethyl)sulfonium chloride and N-(p-methoxybenzylidene)aniline, respectively, with equimolecular proportions ,of dimethyl(N-n-propylcarbamoylmethyl)sulfonium chloride and benzalaniline there is obtained B-anilino-Nn-propylcinnamide which melts at 112-113" C.
EXAMPLE XI Employing the procedure of Example I but replacing N,N-diethyl-u-chloroacetamide with an equimolecular amount of ethyl a-bromoacetate there is obtained dimethyl(ethoxycarbonylmethyl)sulfonium bromide.
onm-s-om-i'z-ooirrfinr which melts at 85-87 C.
EXAMPLE XII Employing the procedure of Example H but replacing dimethyl(N,N diethylcarhamoylmethyl)sulfonium chloride and N-(p-methoxybenzylidene), respectively, with equimolecular proportions of dimethyl(ethoxycarbonylmethyl)sulfonium bromide and benzalaniline there is obtained ethyl ,B-anilinocinnamate which melts at 6768 C.
EXAMPLE XIII Employing the procedure of Example I but replacing N,N-diethyl-u-chloroacetamide with an equimolecular amount of isopropyl a-chloroacetate there is obtained dimethyl(isopropoxycarhonylmethyl sulfonium chloride.
EXAMPLE XIV Employing the procedure of Example II but replacing dimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride with an equimolecular amount of dimethyl(isopropoxycarbonylmethyl)sulfonium chloride there is obtained isopropyl fl-anilindp-methoxycinnamate.
EXAMPLE XV To a concentrated aqueous solution of dimethyl(N,N- diallylcarbamoylmethyl)sulfonium chloride is added in small increments an equimolecular amount of potassium iodide while agitating at room temperature. The mass is filtered and the filter cake dried under anhydrous nitrogen to give dimethyl(N,N-diallylcarbamoylmethyl)sulfonium iodide which melts at 103-105 C. 7
EXAMPLE XVI Employing the procedure of Example XV but replacing dimethyl(N,N diallylcarbamoylmethyl)sulfonium ch10- ride with an equimolecular amount of dimethyl(N,N-diethylcarbamoylmethyl)sulfonium chloride there is obtained dimethyl(N,N-diethylcarbamoylmethyl)sulfonium iodide.
EXAMPLE XVII Employing the procedure of Example XV but replacing dimethyl(N,N diallylcarbamoylmethyl)sulfonium chloride with an equimolecular amount of dimethyl(ethoxycarbonylmethyDsulfoniurn bromide there is obtained dimethyl (ethoxycarbonylmethyl) sulfonium iodide.
EXAMPLE XVIII Employing the procedure of Example I but replacing N,N-diethyl-a-chloroacetamide with an equimolecular amount of N-allyl-u-chloroacetamide there is obtained dimethyl(N-allylcarbamoylmethyl)sulfonium chloride.
EXAMPLE XIX Employing the procedure of Example I but replacing dimethyl sulfide with an equimolecular amount of diethyl sulfide there is obtained diethyl(N,N-diethylcarbamoylmethyl)su1fonium chloride.
EXAMPLE XX Employing the procedureof Example I but replacing dimethyl sulfide with an equimolecular amount of n-butylmethyl sulfide (i.e., n-C H -SCH there is obtained 11 butylmethyl(N,N diethylcarbamoylmethyl) sulfonium EXAMPLE XXI Employing the procedure of Example I but replacing N,N-diethyl-a-chloroacetamide with an equimolecular amount of N-methyl-N-isopropyl-a-chloroacetamide there is obtained dimethyl(N-methyl N isopropylcarbamoylmethyl)sulfonium chloride.
EXAMPLE XXII Employing the procedure of Example I but replacing N,N-diethyl-a-chloroacetamide with an equimolecular amount of N,N-di(2-ethoxyethyl)-u-chloroacetamide there is obtained dimethyl[N,Ndi(2-ethoxyethy1)carbamoylmethyl]sulfonium chloride.
EXAMPLE XXIII Employing the procedure of Example 11 but replacing N-(p-methoxybenzylidene)aniline with an equimolecular amount of benzal-p-anisidine there is obtained fl-p-anisidino-N,N-diethylcinnamide EXAMPLE XXIV Employing the procedure of Example II but replacing N-(p-methoxybenzylidene)aniline with an equimolecular amount of benzal-p-methoxy-o-toluidine there is obtained fl-(p-methoxy-o-toluidino)-N,N-diethylcinnamide.
EXAMPLE XXV Employing the procedure of Example II but replacing N-(p-methoxybenzylidene)aniline with an equimolecular amount of N-(p-methoxybenzylidene)-p-toluidine there is obtained fl-(p-toluidino)-N,N-diethyl-p-ethoxycinnamide.
EXAMPLE )Q(VI Employing the procedure of Example II but replacing dirnethyl(N,N diethylcarbamoylmethyl)sulfonium chloride with an equimolecular amount of dimethyl(N-allylcarbamoylmethyl)sulfonium chloride there is obtained 13- anilino-N-allyl-p-methoxycinnamide.
EXAMPLE XXVII Employing the procedure of Example II but replacing dimethyl (N,N diethylcarbamoylmethyl) sulfonium chloride and N-(p-methoxybenzylidene)aniline, respectively, with equimolecular proportions of dimethyl(N-methyl-N- isopropylcarbamoylmethyl)sulfonium chloride and benzalaniline there is obtained fl-anilino-N-methyl-N-isopropylcinnamide.
EXAMPLE XXVIII Employing the procedure of Example II but replacing dimethyl (N,N diethylcarbamoylmethyl)sulfonium chloride and N-(p-methoxybenzylidene)aniline, respectively, with equimolecular proportions of dimethyl[N,N-di(2- ethoxyethyl)carbamoylmethyl]sulfonium chloride and N- (m,p-dimethoxybenzylidene)aniline there is obtained anilino-N,N-di(2-ethoxyethyl)-m,p-dimethoxycinnamide.
EXAMPLE XXIX Employing the procedure of Example II but replacing dimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride and N-(p-methoxybenzylidene)aniline, respectively, with equimolecular proportions of dimethyl(N,N-diallylcarbamoylmethyl)sulfoniurn iodide and benzal-p-tert.butylaniline there is obtained fi-(p-tertbutylanilino)-N,N- diallylcinnamide.
EXAMPLE XXX Employing the procedure of Example 11 but replacing dimethyl(N,N diethylcarbamoylmethyl)sulfonium chloride and N-(p-methoxybenzylidene)aniline, respectively, with equimolecular proportions of dimethyl(ethoxycarbonylmethyl) sulfonium iodide and benzal o toluidine there is obtained ethyl p-(o-toluidino)-cinnamate.
Other sulfonium halides and B-arylamino cinnamoyl compounds which can be prepared in accordance with the procedures of this invention include methylethyl (N,N-diallylcarbamoylmethyl sulfonium chloride,
methylethyl (N,N-dimethylcarbamoylmethyl) sulfonium chloride,
diisopropyl(N,N-diallylcarbamoylmethyl sulfonium chloride,
di-n-butyl (N,N-diallylcarbamoylmethyl sulfonium chloride,
dimethyl (methoxycarbonylmethyl) sulfonium chloride,
diethyl (ethoxycarbonylmethyl) sulfonium chloride,
methylethyl (ethoxycarbonylmethyl) sulfonium chloride,
methylethyl (isopropoxycarbonylmethyl) sulfonium chloride,
diisopropyl (methoxycarbonylmethyl sulfonium chloride,
di-n-butyl (isobutoxycarbonylmethyl) sulfonium chloride,
and the corresponding sulfonium bromides and sulfonium iodides;
B-anilino-N-methylcinnamide, 18-anilino-N-ethylcinnamide, B-anilino-N-isopropylcinnamide, fl-anilino-N-n-butylcinnamide, fi-anilino-N,N-dimethylcinnamide, fl-anilino-N,N-dimethyl-p-ethoxycinnamide, B-anilino-N,N-di-n-butylcinnamide, fl-anilino-N-allylcinnamide, fl-anilino-N-allyl-o-methylcinnamide, S-anilino-N-(2-rnethoxyethyl)cinnamide, fi-anilino-N,N-di-n-propylcinnamide, fl-anilino-N,N-dibut-2-enylcinnamide,
[3- (o-toluidino) -N,N-diallylcinnamide, fl-(anisidino)-N,N-diallylcinnamide, fl-(p-anisidino) -N,N-diallyl-p-isobutoxycinnamide, B-(m-phenetidino)-N-allylcinnamide,
,B- (m-phenetidino -N-allyl-p-isopropylcinnamide, fi-(m-phenetidino)-N-isopropylcinnamide,
B- (p-isopropylanilino -N,N-dimethylcinnamide, p- (m,p-diethoxyanilino -N,N-dimethylcinnamide, fi- (p-isobutoxyanilino) -N,N-di-n-propylcinnamide, 8- (o-anisidino -N- (Z-methoxyethyl )cinnamide,
,8- (p-anisidino) -N-'methyl-N-isopropylcinnamide, fl- (p-toluidino -N-methyl-N-isopropylcinnamide, methyl fi-anilinocinnamate,
ethyl fl-anilino-p-isopropylcinnamate,
isopropyl fi-anilinocinnamate,
isopropyl B-anilino-m-ethoxycinnamate,
n-butyl B-anilinocinnamate,
methyl [3-(m-anisidin0)cinnamate,
ethyl S-(p-phenetidino) cinnamate,
methyl B-(m,p-dimethoxyanilino cinnamate, ethyl ,3- (p-isobutoxyanilino cinnamate,
and the like.
The effectiveness of the compounds of this invention as fungicides is illustrated below.
Slide germination test.--By the slide germination test the concentration of the compound to be evaluated required to inhibit complete germination of spores from 7- to 10-day old cultures of Venturia inaequalis is determined. 1.0 gram of the compound (below itemized) is dissolved in acetone to make a concentrated solution thereof and thereto is added and intimately mixed 0.] gram of sorbitan monolaurate polyoxyethylene derivative (a commercial water-soluble non-ionic emulsifying agent). Thereto is added and intimately mixed sufficient water to provide an aqueous emulsion containing 10 p.p.m. of the compound. To a test tube is then added four volumes of the aqueous emulsion and one volume of spore stimulant and one volume of spore suspension, the spore stimulant being added to insure a high and relatively stable percentage of germination in the control. Drops of the test specimen mixture and an untreated control are pipetted onto glass slides. The glass slides are then placed in moist chambers for hours incubation at 22 C. Germination counts are made by counting 100 potentially viable spores, i.e. those spores which would germinate under the normal conditions of the control. The results were as follows:
Compound: Germination Dimethyl(N,N-diallylcarbamoylmethyl) sulfonium bromide None Dimethyl(N,N-diallylcarbamoylmethyl) sulfonium iodide None Dimethyl(N,N-diallylcarbamoylmethyl) sulfoniurn chloride None Dimethyl (N-n-propylcarbamoylmethyl) sulfonium chloride None B-Anilino-N,N-diethylcinnamide None B-Anilino-N,N-diallylcinnamide None Control Complete In a similar evaluation against the late blight fungus Phytophthora infestans at respective concentrations of 10 p.p.m. dimethyl(N,N diallylcarbamoylmethyl)sulfonium bromide, dimethyl(N n propylcarbamoylmethyl)sulfonium chloride and B-anilino -N,N diethylcinnamide, respectively, completely prevented germination of spores of said fungus.
With respect to the soil fungus Pythium ultz'mum at a concentration of 30 p.p.m. dimethyl(N,N-diallylcarbamoylmethyl)sulfonium bromide and [3-anilino-N,N-diethylp-methoxycinnamide, respectively, exhibited complete control of the said soil fungus.
As aforementioned the alkyl ,B-arylamino cinna'mates of this invention effectively control mosquito larvae. For example at a concentration of 10 p.p.m. ethyl 8-anilinocinnamate exhibited a kill of yellow fever mosquito larvae, Aedes aegypti.
The exact concentration of the fungicidal or insecticidal agents of this invention employed in combatting or controlling fungi o'r insects can vary considerably provided the required dosage (i.e., a toxic amount) thereof is supplied to the respective organisms or to the environment of the organisms. When the extending agent is a liquid or mixture of liquids (e.g. as in solutions, suspensions, emulsions, or aerosols) the concentration of the fungicidal or insecticidal agent employed to supply the desired dosage generally will be in the range of 0.001 to 50 percent by weight. When the extending agent is a semi-solid or solid, the concentration of the fungicidal or insecticidal agent employed to supply the desired dosage generally will be in the range of 0.1 to 25 percent by weight. From a practical point of view, the manufacturer must supply the agriculturist with a low-cost concentrate or spray base or particulate solid base in such form that, by merely mixing with water or solid extender (e.g., powdered clay or talc) or other low-cost material available to the agriculturist at the point of use, he will have an easily prepared fungicidal or insecticidal spray or particulate solid. In such a concentrate composition, the fungicidal or insecticidal agent generally Will be present in a concentration of 5 to percent by weight, the residue being any one or more of the well-known fungicidal or insecticidal adjuvants, such as the various surface active agents (e.g., detergents, a soap or other emulsifying or wetting agent, surface-active clays), solvents, diluents, carrier media, adhesives, spreading agents, humectants, and the like.
In controlling or combatting fungal organisms or insects the fungicidal or insecticidal agents of this invention either per se or compositions comprising same are supplied to the fungi or insects or to their environment in a toxic amount. This can be done by dispersing the new fungicidal or insecticidal agent or fungicidal or insecticidal composition comprising same in, on or over an infested environment or in, on or over an environment the fungi or insects frequent, e.g. agricultural soil or other growth media or other media infested with the fungi or insects, or attractable to the fungi or insects for habitational or sustenance or propagational purposes, in any conventional fashion which permits contact between the organisms and the fungicidal or insecticidal agents of this invention. Such dispersing can be brought about by applying the fungicidal agent per se or sprays or particulate solid compositions containing same to a surface infested with the fungi or insects or attractable to same, as for example, the surface of agricultural soil or other media such as the above ground surface of plants by any of the conventional methods, e.g. power dusters, boom and hand sprayers, and spray dusters. Also for sub-surface application such dispersing can be carried out by simply mixing the new fungicidal or insecticidal agent per se or fungicidal or insecticidal spray or particulate solid compositions comprising same with the infested environment or with the environment the fungi or insects frequent, or by employing a liquid carrier for the new fungicidal 0r insecticidal agent to accomplish sub-surface penetration and impregnation therein.
What is claimed is:
l. The method of controlling Ven turia inaequalis which comprises contacting same with a fungicidally toxic amount of a sulfonium chloride of the formula RQ R e s-cm-c-a/ 01 wherein R" and R'" are C alkyl and wherein R and R are like lower n-alkyl.
2. The method of controlling Venturia inaequalis which comprises contacting same with a fungicidally toxic amount of a sulfonium chloride of the formula wherein R" and R' are C alkyl and wherein R and R are like lower n-alkenyl.
3. The method of controlling Venturiw inaequalis which comprises contacting same with a fungicidally toxic amount of dimethyl(N,N diallylcarbamoylmethyl)sulfonium chloride.
References Cited UNITED STATES PATENTS 3,102,068 8/ 1963 Talbert 16722 FOREIGN PATENTS 1,035,397 7/ 1958 Germany.
OTHER REFERENCES Chemical Abstracts (I), vol. 47, pp. 3382(i)-3883(a), 1953.
Chemical Abstracts (H), vol. 53, p. 3192(a), 1959.
Papavigas et al.: Phytopathology, vol. 53, 1963, pp. 109-115.
FRANK CACCIAPAGLIA, 1a., Primary Examiner US. Cl. X.R-.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US46775065A | 1965-06-28 | 1965-06-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3478154A true US3478154A (en) | 1969-11-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US3478154D Expired - Lifetime US3478154A (en) | 1965-06-28 | 1965-06-28 | Fungicidal (n-substituted carbamoylmethyl) sulfonium chlorides |
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| Country | Link |
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| US (1) | US3478154A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686279A (en) * | 1964-07-09 | 1972-08-22 | Giffin D Jones | 2-methylene-3-butenyl sulfonium salts useful as monomers |
| US4556737A (en) * | 1983-03-11 | 1985-12-03 | Taiho Pharmaceutical Company Limited | Sulfonium compounds, processes for preparing the compounds and pharmacological composiitons containing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1035397B (en) * | 1956-03-23 | 1958-07-31 | Bayer Ag | Process for improving the solubility of protective agents against keratin pests |
| US3102068A (en) * | 1961-10-10 | 1963-08-27 | Michigan State University Of A | Method of controlling bacterial diseases of fruit trees |
-
1965
- 1965-06-28 US US3478154D patent/US3478154A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1035397B (en) * | 1956-03-23 | 1958-07-31 | Bayer Ag | Process for improving the solubility of protective agents against keratin pests |
| US3102068A (en) * | 1961-10-10 | 1963-08-27 | Michigan State University Of A | Method of controlling bacterial diseases of fruit trees |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3686279A (en) * | 1964-07-09 | 1972-08-22 | Giffin D Jones | 2-methylene-3-butenyl sulfonium salts useful as monomers |
| US4556737A (en) * | 1983-03-11 | 1985-12-03 | Taiho Pharmaceutical Company Limited | Sulfonium compounds, processes for preparing the compounds and pharmacological composiitons containing the same |
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